Carbazolic Conjugated Microporous Polymers for Photocatalytic Organic Transformations.

Heterogeneous photocatalysis have been deemed as a versatile and colorful platform for exploring efficient transformation systems. Henceforth, the design of photocatalysts underpins a wide range of research interests. By virtue of synthetic versatility, stability, non-toxicity, purely organic properties, tunable semiconductive structures, and remarkable visible-light absorbance, conjugated microporous polymers (CMPs) have emerged as an attractive new class of semiconductor materials that show great potential for tackling important energy and environmental challenges. Over the past decade, immense efforts have been devoted toward the construction of CMPs-based photocatalysts for versatile photocatalytic transformations. This review aims to summarize the latest representative advances in the field of carbazolic CMPs, focusing on various design strategies for the construction of tailor-made skeletons that have direct impact on their charge dynamics and thus photocatalytic performances, especially on their specific photocatalytic efficiency for organic transformations. Scrutinizing the photocatalytic features and elucidating the related design principles, it is fully described how structure modification of polycarbazoles could have an effect on optical properties, and thus on photocatalytic performance. Furthermore, the bottlenecks that need to be addressed, and the future research directions of CMPs are identified in the area of photocatalysis.

Mixing Characteristic and High-Throughput Synthesis of Cadmium Sulfide Nanoparticles with Cubic Hexagonal Phase Junctions in a Chaotic Millireactor.

A four-stage oscillating feedback millireactor with splitters (S-OFM) was designed to improve the mixing performance based on chaotic advection. Three-dimensional CFD simulations were used to investigate its flow characteristics and mixing performance, and the generation mechanisms of secondary flows were examined. The results show that the mixing index (MIcup) increased with the increase in the Reynolds number (Re), and MIcup could reach 99.8% at Re = 663. Poincaré mapping and Kolmogorov entropy were adopted to characterize the chaotic advection intensity, which indicates that there is a intensity increase with the increase in Re. In addition, the results of Villermaux-Dushman experiments demonstrate that S-OFM performs excellently, and the mixing time could reach 1.04 ms at Re = 2764. Finally, S-OFM was successfully used to synthesize CdS nanoparticles with cubic hexagonal phase junctions. At a flow rate of 180 mL/min, the average particle size was 10.5 nm and the particle size distribution was narrow (with a coefficient of variation of 0.14).

Enhanced photocatalytic activity of the direct Z-scheme black phosphorus/BiOX (X = Cl, Br, I) heterostructures.

Bismuth oxyhalides (BiOX), as a typical photocatalytic material, have attracted much attention due to their unique layered structure, non-toxicity and excellent stability. However, the photocatalytic performance of BiOX is limited by their weak light absorption ability and rapid recombination of photo-generated carriers. In the present work, first-principles calculations have been performed to comprehensively explore the structural, electronic and optical properties of black phosphorus (BP)/BiOX (X = Cl, Br, I) heterostructures, revealing the inherent reasons for their enhanced photocatalytic performance. By combining band structures and work function analysis, the migration paths of photo-generated electrons and holes are obtained, proving a direct Z-scheme photocatalytic mechanism in BP/BiOX heterostructures. Moreover, the BP/BiOX heterostructures have decent band edge positions, which are suitable for photocatalytic overall water splitting. Compared with single BiOX, the light absorption performance of BP/BiOX heterostructures is significantly improved, in which BP/BiOI exhibits the highest optical absorption coefficient among the BP/BiOX heterostructures. Meanwhile, the better carrier migration performance of the BP/BiOX heterostructures is attributed to the reduction in effective mass. The present work offers theoretical insight into the application of BP/BiOX heterostructures as prominent photocatalysts for water splitting.

Thickness-induced band-gap engineering in lead-free double perovskite Cs2AgBiBr6 for highly efficient photocatalysis.

In recent years, two-dimensional (2D) lead-free double perovskites have been attracting much attention because of their unique performance in photovoltaic solar cells and photocatalysis. Nonetheless, how thickness affects the photoelectric properties of lead-free double perovskite remains unclear. In this work, by means of density functional theory (DFT) with a spin orbit coupling (SOC) effect, we have investigated the electronic and optical properties systemically, including band structures, carrier mobility, optical absorption spectra, exciton-binding energies, band edges alignment and molecule adsorption performance of Cs2AgBiBr6 with different thicknesses. The calculated results revealed the thickness-induced band gap and optical performance for Cs2AgBiBr6. It shows a low band gap and outstanding optical absorption of visible and ultraviolet light. When the thickness is reduced to a monolayer, Cs2AgBiBr6 moves from an indirect band gap to a direct band gap. Moreover, the carrier mobility of Cs2AgBiBr6 is excellent and the exciton-binding energy increases with the decreased thickness. Importantly, an analysis of molecule adsorption and band edge alignment indicates that Cs2AgBiBr6 is prone to H2O adsorption and H2 desorption theoretically, which is conducive to the photocatalytic water splitting for hydrogen generation and other photovatalytic reactions. Our work suggests that Cs2AgBiBr6 is a potential candidate as a solar cell or a photocatalyst, and we provide theoretical explorations into reducing the layers of lead-free double perovskite materials to 2D atomic thickness for a better photocatalytic application, which can serve as guidelines for the design of excellent photocatalysts.

Activity and Stability Boosting of an Oxygen-Vacancy-Rich BiVO4 Photoanode by NiFe-MOFs Thin Layer for Water Oxidation.

The introduction of oxygen vacancies (Ov) has been regarded as an effective method to enhance the catalytic performance of photoanodes in oxygen evolution reaction (OER). However, their stability under highly oxidizing environment is questionable but was rarely studied. Herein, NiFe-metal-organic framework (NiFe-MOFs) was conformally coated on oxygen-vacancy-rich BiVO4 (Ov-BiVO4 ) as the protective layer and cocatalyst, forming a core-shell structure with caffeic acid as bridging agent. The as-synthesized Ov-BiVO4 @NiFe-MOFs exhibits enhanced stability and a remarkable photocurrent density of 5.3±0.15 mA cm-2 at 1.23 V (vs. RHE). The reduced coordination number of Ni(Fe)-O and elevated valence state of Ni(Fe) in NiFe-MOFs layer greatly bolster OER, and the shifting of oxygen evolution sites from Ov-BiVO4 to NiFe-MOFs promotes Ov stabilization. Ovs can be effectively preserved by the coating of a thin NiFe-MOFs layer, leading to a photoanode of enhanced photocurrent and stability.

Nickel-Catalyzed Decarbonyloxidation of 3-Aryl Benzofuran-2(3H)-ones to 2-Hydroxybenzophenones.

We have developed a protocol to facilitate the nickel-catalyzed decarbonyloxidation of 3-aryl benzofuran-2(3H)-ones to 2-hydroxybenzophenones under mild conditions, which is an efficient approach for the decarbonyloxidation of lactones in organic synthesis. A diverse range of substrates can undergo C(O)-O/C(O)-C bond cleavage to generate the target products in good yields. These 2-hydroxybenzophenones can be converted into a variety of compounds via reactions such as esterification, cyclization, and reduction.

Iodine-Catalyzed Synthesis of N,N'-Chelate Organoboron Aminoquinolate.

We disclose a novel method for the synthesis of fluorescent N,N'-chelate organoboron compounds in high efficiency by treatment of aminoquinolates with NaBAr4/R'COOH in the presence of an iodine catalyst. These compounds display high air and thermal stability. A possible catalytic mechanism based on the results of control experiments has been proposed. Fluorescence quantum yield of 3b is up to 0.79 in dichloromethane.

Iron-Based Metal-Organic Frameworks as Platform for H2S Selective Conversion: Structure-Dependent Desulfurization Activity.

Three classical Fe-MOFs, viz., MIL-100(Fe), MIL-101(Fe), and MIL-53(Fe), were synthesized to serve as platforms for the investigation of structure-activity relationship and catalytic mechanism in the selective conversion of H2S to sulfur. The physicochemical properties of the Fe-MOFs were characterized by various techniques. It was disclosed that the desulfurization performances of Fe-MOFs with well-defined microstructures are obviously different. Among these, MIL-100(Fe) exhibits the highest catalytic performance (ca. 100% H2S conversion and 100% S selectivity at 100-180 °C) that is superior to that of commercial Fe2O3. Furthermore, the results of systematic characterization and DFT calculation reveal that the difference in catalytic performance is mainly because of discrepancy in the amount of Lewis acid sites. A plausible catalytic mechanism has been proposed for H2S selective conversion over Fe-MOFs. This work provides critical insights that are helpful for rational design of desulfurization catalysts.

Carbon-Carbon Bond Formation of Trifluoroacetyl Amides with Grignard Reagents via C(O)-CF3 Bond Cleavage.

The reaction of trifluoroacetyl amides with Grignard reagent for the substitution of CF3 group with various alkyl or aryl groups is described. A variety of aryl, quinolin-8-yl, and (hetero)alkyl functional groups as well as F, Cl, and Br atoms are well tolerated. These moisture-stable and easily available trifluoroacetyl amides can be conveniently obtained and used as new versatile precursors for isocyanates. The control experiments show that the reaction proceeds via an isocyanate intermediate and/or alkoxide/amide dual anionic intermediate.

Cetyltrimethyl ammonium bromide catalysed oxidative cross dehydrogenative coupling of benzylic C(sp3)-H bonds in methylarenes with P(O)-OH compounds.

An efficient metal-free method for the synthesis of organophosphorus compounds via oxidative cross dehydrogenative coupling of benzylic C(sp3)-H bonds in methylarenes with P(O)-OH compounds catalysed by cetyltrimethyl ammonium bromide (CTAB) is reported. Various methylarenes and P(O)-OH compounds are tolerated in the reaction with moderate to good yields. Compared to previous studies, the present study extends the substrate scope and adopts a new reaction system of an ammonium salt catalyst (CTAB) and an oxidant (DTBP). The results of control and mechanistic experiments are generally in agreement with the overall proposed pathway. This method circumvents the use of toxic P-halogen reagents and P(O)-H compounds for the synthesis of organophosphorus compounds.

Amino-Modified Fe-Terephthalate Metal-Organic Framework as an Efficient Catalyst for the Selective Oxidation of H2S.

Classical amino-functionalized Fe-terephthalate metal-organic framework NH2-MIL-53(Fe) and its parent framework MIL-53(Fe) were prepared via simple hydrothermal methods. The catalytic performaces of these two Fe-MOFs were explored for the selective oxidation of H2S. The physicochemical properties of the fresh and used Fe-MOFs catalysts were investigated by XRD, BET, SEM, FT-IR, CO2-TPD, and XPS techniques. It was found that the introduction of amino groups reduces the activation energies for H2S oxidation and endows this catalyst surface with moderate basic sites. As a result, the NH2-MIL-53(Fe) catalyst displays high H2S conversion and near 100% S selectivity in the temperature range of 130-160 °C, outperforming commercial Fe2O3 and activated carbon. Moreover, a plausible reaction route for H2S selective oxidation over NH2-MIL-53(Fe) is proposed. This work opens up the possibility of utilizing MOFs as efficient catalyst for desulfuration reactions.

Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature.

A protocol for the chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder under an oxygen atmosphere is reported. This reaction proceeds efficiently to afford fully substituted unsymmetrical N-arylation phosphinamides at room temperature in excellent yields. Diverse unstable functional groups on the benzene ring of aryl boronic acids such as vinyl, formyl, acetyl, sulfonyl, acetylamino, cyano, nitro, and trifluoromethyl can be accommodated.

Construction and Application of a Non-Enzyme Hydrogen Peroxide Electrochemical Sensor Based on Eucalyptus Porous Carbon.

Natural eucalyptus biomorphic porous carbon (EPC) materials with unidirectional ordered pores have been successfully prepared by carbonization in an inert atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) were employed to characterize the phase identification, microstructure and morphology analysis. The carbon materials were used to fabricate electrochemical sensors to detect hydrogen peroxide (H2O2) without any assistance of enzymes because of their satisfying electrocatalytic properties. It was immobilized on a glassy carbon electrode (GCE) with chitosan (CHIT) to fabricate a new kind of electrochemical sensor, EPC/CHIT/GCE, which showed excellent electrocatalytic activity in the reduction of H2O2. Meanwhile, EPC could also promote electron transfer with the help of hydroquinone. The simple and low-cost electrochemical sensor exhibited high sensitivity, and good operational and long-term stability.

Nickel-Catalyzed Regioselective Cleavage of C(sp(2))-S Bonds: Method for the Synthesis of Tri- and Tetrasubstituted Alkenes.

We describe here an efficient route for the synthesis of (Z)-vinylic sulfides 3 via the highly regio- and stereoselective coupling of (Z)-1,2-bis(aryl(alkyl)thio)alkenes and Grignard reagents over a Ni catalyst under mild conditions. (Z)-Vinylic sulfides 3 are important intermediates in the synthesis of tri- and tetrasubstituted alkenes that are important construction blocks for drugs and natural products. The directing organosulfur groups (SR) can be converted to diaryl(alkyl) disulfides (RSSR) using H2O2 as oxidant, hence avoiding the waste of sulfur resources. The protocol provides a general method that is highly regio- and stereoselective for the synthesis of a diversity of tri- and tetrasubstituted alkenes.

Efficient synthesis of propargylamines from terminal alkynes, dichloromethane and tertiary amines over silver catalysts.

A simple, efficient and highly functional group compatible method for the synthesis of propargylamines from terminal alkynes, dichloromethane and tertiary amines using silver catalysts has been developed.

Enhanced exchange bias and coercivity arising from heterojunctions in Ni-NiO nanocomposites.

By a reflux process, we prepared Ni-NiO nanocomposites that are face-centered cubic (fcc). By tuning the precursor concentration, we controlled the Ni content in the Ni-NiO nanocomposites. We found that both the interface of Ni and NiO crystal lattices and the weight fraction of Ni have significant impacts on their magnetic properties. There is increase of saturation magnetization and decrease of coercivity (HC) with the increase of the Ni weight fraction. Large exchange bias (HE) and enhanced HC are observed at 5 K, which are due to the creation of heterojunctions at the interfaces of ferromagnetic Ni and antiferromagnetic NiO. After optimization, it is observed that the Ni-NiO nanocomposites with an Ni content of 2.6% show an HC and HE of 1068 and 350 Oe, respectively.

Strong morphological effect of Mn3O4 nanocrystallites on the catalytic activity of Mn3O4 and Au/Mn3O4 in benzene combustion.

Gold nanoparticles (3-4 nm) were deposited on Mn3O4 nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn3O4 polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn3O4 facet: Au/(200)≈Au/(103)>Au/(101). The metal-support interactions between the Au nanoclusters and specific facets of the Mn3O4 polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn3O4 substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn3O4 system.

Room-temperature synthesis of flower-like BiOX (X═Cl, Br, I) hierarchical structures and their visible-light photocatalytic activity.

A simple method for facile synthesis of three-dimensional (3D) bismuth oxyhalide (BiOX, X═Cl, Br, I) hierarchical structures at room temperature has been developed. Under the influence of L-lysine surfactant, the bismuth and halogen (Cl, Br, I) sources hydrolyze and self-assemble into flower-like hierarchical architectures within 10 min. The resulted materials were characterized by XRD, FESEM, TEM, UV-vis DRS, and N2 adsorption-desorption techniques. We found that l-lysine is indispensable for their formation and the amount of HX has great effect on the final morphology. The BiOX (X═Cl, Br, I) hierarchical architectures are composed of single-crystalline nanoplates. We propose an amino-and-carboxyl structure-directing mechanism for the formation of the hierarchical structures. To evaluate the photocatalytic activity of the as-prepared materials, rhodamine-B was employed as a probe dye for degradation under visible light. All of the BiOX (X═Cl, Br, I) with 3D architectures show higher photocatalytic activities than their sheet-like counterparts. The superior activity is ascribed to the better light-harvesting capacity of the 3D hierarchical structures. The adopted method can be applied for large-scale generation of novel structures of similar kinds in a facile manner.

Porous FeOx/BiVO4-deltaS0.08: highly efficient photocatalysts for the degradation of methylene blue under visible-light illumination.

Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide (y wt.% FeOx/BiVO4-deltaS0.08, y = 0.06, 0.76, and 1.40) photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-deltaS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi5+, Bi3+, V5+, V3+, Fe3+, and Fe2+ species in y wt.% FeOx/BiVO4-deltaS0.08. The 1.40 wt.% FeOx/BiVO4-deltaS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower bandgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-deltaS0.08.

Hydrothermal fabrication and visible-light-driven photocatalytic properties of bismuth vanadate with multiple morphologies and/or porous structures for methyl orange degradation.

Monoclinic BiVO4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO4 product. Spherical BiVO4 with porous structures, flower-cluster-like BiVO4, and flower-bundle-like BiVO4 were generated hydrothermally at 100 degrees C with poly(vinyl pyrrolidone) (PVP) and urea (pH = 2) and at 160 degrees C with NaHCO3 (pH = 7 and 8), respectively. The PVP-derived BiVO4 showed much higher surface areas (5.0-8.4 m2/g) and narrower bandgap energies (2.45-2.49 eV). The best photocatalytic performance of the spherical BiVO4 material with a surface area of 8.4 m2/g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.